CN102782474A - Intelligent pigments and plastics - Google Patents

Intelligent pigments and plastics Download PDF

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Publication number
CN102782474A
CN102782474A CN2010800570039A CN201080057003A CN102782474A CN 102782474 A CN102782474 A CN 102782474A CN 2010800570039 A CN2010800570039 A CN 2010800570039A CN 201080057003 A CN201080057003 A CN 201080057003A CN 102782474 A CN102782474 A CN 102782474A
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indicator
chemical indicator
reactive dye
polymer composites
polymer
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CN102782474B (en
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安德鲁·米尔斯
保尔林·格罗斯汉斯
格林厄姆·斯金纳
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University of Strathclyde
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G01N31/223—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating presence of specific gases or aerosols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/105—Esters; Ether-esters of monocarboxylic acids with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G01N31/223—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating presence of specific gases or aerosols
    • G01N31/225—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating presence of specific gases or aerosols for oxygen, e.g. including dissolved oxygen
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—Specially adapted to detect a particular component
    • G01N33/004—Specially adapted to detect a particular component for CO, CO2
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—Specially adapted to detect a particular component
    • G01N33/0054—Specially adapted to detect a particular component for ammonia
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/02—Food
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/15—Medicinal preparations ; Physical properties thereof, e.g. dissolubility
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/7769—Measurement method of reaction-produced change in sensor
    • G01N2021/7786—Fluorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/7793—Sensor comprising plural indicators
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/7796—Special mountings, packaging of indicators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/17—Nitrogen containing
    • Y10T436/173845—Amine and quaternary ammonium
    • Y10T436/175383—Ammonia
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/20—Oxygen containing
    • Y10T436/204998—Inorganic carbon compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/20—Oxygen containing
    • Y10T436/207497—Molecular oxygen

Abstract

A chemical indicator comprises a particulate inorganic substrate, and at least one reactive dye or ink coated on and/or impregnated within the particulate inorganic substrate. Coating and/or impregnating at least one reactive dye or ink on or within a particulate inorganic substrate improves the storage stability and/or thermal stability of the at least one reactive dye or ink, which typically comprises relatively unstable compounds. This allows the present indicators to be incorporated into thermoplastic polymer materials and processed conventionally while maintaining the efficacy and stability of the new indicators. The indicators provide simple, reliable, and cost effective detection means for detecting analytes such as ammonia, carbon dioxide, and oxygen, and may find use in applications such as food packaging and medical applications.

Description

Intelligence pigment and plastics
Invention field
The present invention relates to chemical indicator, said chemical indicator comprises the particle inorganic matrix; And at least a reactive dye or China ink, said at least a reactive dye or China ink are coated on the said particle inorganic matrix or are immersed in the said particle inorganic matrix.
The invention still further relates to the method for this chemical indicator of preparation, said method is included as the particle inorganic matrix at least a reactive dye or China ink is provided.
The invention still further relates to a kind of polymer composites, said polymer composites comprises at least a polymkeric substance, and one or more this chemical indicators.
The invention still further relates to the method for this polymer composites of preparation, said method comprises provides one or more this chemical indicators at least a polymkeric substance.
The invention still further relates to this polymer composites and for example breathe the purposes in the medical science in packaging for foodstuff and/or medical science.
Background of invention
The colorimetric indicator is to be used for detecting any means known that chemical substance exists at particular medium.Such indicator comprises, for example, the pH indicator, when the pH of the medium of wherein putting into said pH indicator changed, the pH indicator represented change color.
This indicator depends on the optical characteristics of reactive dye or China ink.These dyestuffs can exist with at least two kinds of different chemical states, and wherein the dyestuff of every kind of form absorbs the light in the particular range of wavelengths.In the time will being exposed to given material with this reactive dye that first kind of form exists, it becomes the dyestuff of second kind of form thus via reversible chemical reaction and this substance reaction.Because the dyestuff of second kind of form absorbs the light of different wave length, this chemical reaction provides the observer visible change color.
Therefore, the use of colorimetric indicator is that the problem that detects the existence of some particular chemicals provides attractive solution potentially.
This material comprises gas, and like carbon dioxide, ammonia and oxygen, these gases acquire a special sense at aspects such as packagings for foodstuff.
Detection to carbon dioxide always has importance, this owing to carbon dioxide when keeping excessive concentrations to the negative interaction of health.Medically, carbon dioxide is a kind of key, basic analyte, in the blood of patient in hospital, it is carried out routine monitoring.Carboloy dioxide analysis is a medical domain of being devoted to monitor carbon dioxide level in the breathing specially.The existence of carbon dioxide not only provides important valuable medical information, and via carboloy dioxide analysis, the transient change of carbon dioxide in expiration also is used to provide diagnostic message usually.In anesthesiology, a kind of method that the pipe that assurance will be transported gas to lung correctly is placed in the tracheae rather than in the esophagus is the level (in expiration, being generally 4-5%) of monitoring carbon dioxide.
In food industry, the application of controlled atmospheric packing (MAP) is of long duration.The MAP packing relates to oxygenless gas (being generally carbon dioxide) purge food and sealing, in order to being distributed to wholesale and/or the retailer.The purpose of MAP packing is to prevent the aerobic growth of microorganism that addles, and makes the safe time of food be extended for 3-4 doubly usually.Carbon dioxide level in the detection MAP sheathing foodstuff is to showing that the fresh of food is necessary.
Ammonia (NH 3) be corrosivity harmful gas with pungency special odor.It is used to prepare explosive, fertilizer, medicine, household cleaning articles for use widely directly or indirectly, and as industrial cooling medium.Ammonia also makes rotten fishing gear that " addling " taste and smell are arranged with other volatile amines, because when the flesh of fish rots, produce these.Therefore, not only in industry, need the monitoring ammonia gas level, in packaging for foodstuff, especially also need monitor ammonia gas level for the fish packing so that leakage and waste water discharge are monitored.After fish was hunted down and kills, microorganism formed on skin and scale.These are called as special spoilage organisms (SSO), and it produces ammonia and volatility amine by the amino acid that is present in the fish, comprises trimethylamine (TMA) and dimethylamine (DMA).These microbial degradation products are collectively referred to as general volatile basic nitrogen compound (TVB-N).If possible, can measure the freshness of fish through measuring TVB-N.
The main cause of most of food spoilages is an oxygen, because its existence makes countless aerobic food spoilage growth of microorganism also flourishing.Oxygen also makes a lot of food spoilage through enzymic catalytic reaction, as in the brown stain of fruits and vegetables, and broken ascorbic acid and the various fragrance matters of oxidation of changing.The a lot of oxidation food spoilage reactions that comprise lipid oxidation do not need enzyme just can take place.
Reported in the document and can detect the multiple colorimetric indicator that specific analyte exists.The reactive dye that in such indicator, adopt have relatively poor thermal stability and/or pot-life usually, and it is difficult to finished product commercialization and application.For example, reported colorimetric CO 2Detector applies is in breathing medical science.The instance of such business equipment comprises that for example, (Nellcor, Pleasanton is CA) with Mini StatCO for Pedi-Cap 2(Mercury Medical, Clearwater, FL).Yet in case from its packages sealed, take out, the mean lifetime of these indicator under normal atmosphere is very short, and Pedi-Cap is generally about 2 hours, and Mini StatCO 2Be about 24 hours.
In the situation of carbon dioxide, below find to make solvent-borne type solid, dried carbon dioxide sensor become possibility: consisting of phase-transferring agent PTA can be extracted to the colorimetric pH indicator of the anionic form aprotic medium from height polarity the polymer/plasticizer environment of low polarity.The water that combines with dyestuff also is delivered to hydrophobic polymer via PTA.At the thin CO of this plastics 2In the film sensors, the balance of between dyestuff and carbon dioxide, setting up can be represented through following reaction:
Figure BDA00001769902500031
Wherein α ' is the equilibrium constant relevant with technology.Although CO 2Has importance and at CO as analyte 2There are remarkable interests in the indicator aspect, but does not almost have the CO based on color 2Indicator is by commercialization.One of reason that causes this is a this indicator less stable in time.Especially because the relatively poor thermal stability of used consisting of phase-transferring agent and tending to and other sour gas such as NO 2And SO 2React, under ambient air conditions, the most pot-life is shorter than six months reversiblely.
Therefore, need develop new chemical indicator in the prior art, and colorimetric indicator especially, with the detection means of simple, reliable and cost savings that the storage that represents improvement and thermal stability are provided.
In addition, need develop the novel polymer type compound substance that is combined with this indicator in the prior art, said compound substance can keep the effectiveness and the stability of new indicator simultaneously via known preparation of Polymer Processing technology and processing.
Summary of the invention
According to an aspect of the present invention; A kind of chemical indicator is provided; Said chemical indicator comprises particle inorganic matrix and at least a reactive dye or China ink, and said at least a reactive dye or China ink are coated on the said particle inorganic matrix and/or are immersed in the said particle inorganic matrix.
Through such setting, can improve the storage stability and/or the thermal stability of said at least a reactive dye or China ink.
Should understand that the particle inorganic matrix is defined as the matrix of usually being processed by insoluble matter and providing with particle form.This generally includes for example inorganic filler and/or inorganic pigment, and it can be white, transparent or coloured.Should understand that insoluble material is defined as the material that is insoluble to based in solvent water or organic in linguistic context of the present invention; Said based on water or organically be intended to be coated on the particle inorganic matrix in the solvent and/or before being immersed in the particle inorganic matrix, dissolve said at least a reactive dye or China ink.
Therefore, what should understand is, the present invention does not for example relate to, and is coated on macroscopical inorganic matrix as as the China ink on the metal sheet of for example beverage can.
Should understand that reactive dye or China ink are defined as the dyestuff that can exist with at least two kinds of different chemical states, wherein every kind of dyestuff form absorbs the light in the particular range of wavelengths.When this dyestuff is exposed to given material, they can be reversible ground or be second chemical state irreversibly by the reaction of first chemical state, thereby cause visible change color.
Advantageously, this chemical indicator can have high thermal stability, for example at least about 80 ℃, and preferably at least 110 ℃.
Advantageously, this chemical indicator can be dark but all be to have long storage stability under the condition of environmental baseline aspect other, for example at least one week, preferred at least one month, more preferably at least six months, most preferably at least ten two months.
Preferably, this indicator can be than colour pattern indicator or light emitting-type indicator.
Expediently, this particle inorganic matrix can be a powder type.
Typically, the particle inorganic matrix can be an inorganic pigment, for example silicon dioxide, titania, aluminium oxide, magnesium oxide, calcium oxide or zeolite, especially silicon dioxide.
In one embodiment, the particle inorganic matrix can be hydrophobic, for example hydrophobic silica or lyophobic alumina.
It is hydrophobic inherently to understand that term hydrophobic is meant, the matrix that perhaps promptly is modified by hydrophobization, thus for example made matrix hydrophobic by surface modification, for example through the hydrophobic chemical group being attached to the surface of matrix.
In another embodiment, the particle inorganic matrix can be hydrophilic, for example hydrophilic silicon dioxide or hydrophilic aluminium oxide.
Should understand term hydrophilic be meant hydrophilic inherently, the matrix that perhaps promptly is modified by hydrophiling, thus for example made matrix hydrophilic by surface modification, for example through hydrophilic chemical group being attached to the surface of matrix.
In another embodiment again, the particle inorganic matrix can be untreated particle inorganic matrix, for example untreated titania.Through provide like this particle inorganic matrix for example titania can keep its photocatalysis property.
Typically, at least a reactive dye can react in the presence of at least a chemical substance that will detect.
The chemical substance that typically, will detect can be the chemical species that can cause chemical change in the reactive dye.
This chemical substance may reside in the air and himself can be gaseous species, for example carbon dioxide, ammonia or oxygen.Alternatively, this chemical substance can be that particulate material perhaps can be in solution or in the suspending liquid, for example in water.This chemicals itself can be that liquid is like alcohol, solvent etc.
Equally typically, at least a reactive dye can be under the balance between two kinds of chemical specieses or the state at least.
Expediently, at least a reactive dye can represent first color under first chemical species or state, and under second chemical species or state, represent second color.
Preferably, first and second colors can be different.
In one embodiment; At least a reactive dye can be carbon dioxide sensitivity reactive dye such as m-cresol purple (MCP; The hydroxyl triarylmethane), thymolphthalein (3; Two (4-hydroxy-2-methyl-5-third-2-base phenyl)-2-coumarone-1-ketone of 3-), o-cresolphthalein, acryloyl group fluorescein (Acryloly florescein) (AcFl), β-Jia Jisanxingtong (β-methyl umbelliferon) (BMUB), bromthymol blue (BTB; The hydroxyl triarylmethane), 5 ' and 6 '-carboxyl half naphthols fluorescein (5 ' and6 '-Carboxyseminaphtholfluorescein) (c-SNAFL), 5 ' and 6 '-carboxyl half naphthols rhodamine (5 ' and 6 '-Carboxyseminaphtholrhodamine) (c-SNARF), cresol red (CR, o-cresolsulfon-phthalein (o-Cresolsulfonephthalein)), cetyltrimethyl ammonium kation (CTA +), cetyltrimethylammonium hydroxide (CTAH), two lumophore benchmark (Dual lumophore referencing) (DLR), 2-(2; 4-dinitrophenyl azo)-1-naphthols-3; (2-(2 for 6 disulfonic acid; 4-Dinitrophenylaxo)-1-naphthol-3,6disulphonic acid) (DNPA), three (TTA) europium (III) ([Eu (tta) 3]), fluorescein (Fl; Resorcinol phthalein (resorcinolphthalein)), umbelliferone-4-acetate (HCA), 1; Hydroxyl pyrene-3; 6,8-trisulfonic acid (HPTS), dimethyl diaminophenazine chloride (NR, stilbene red (toluylene red)), phenol red (PR; Phenolsulfonphthalein (phenolsulfonphthalein)), rhodamine 6G (R6G), sulfo group rhodamine (Sulforhodamine) 101 (SRh), thymol blue (TB, thymolsulfonphthalein (thymolsulphonephthalein)), Texas Red (texas Red) hydrazine (THR).Should be understood that any other pH susceptibility dyestuff or China ink possibly be suitable for as CO 2The susceptibility reactive dye.
In another embodiment, at least a reactive dye can be ammonia susceptibility reactive dye such as bromophenol blue (BPB, hydroxyl triarylmethane), bromcresol green (BCG; The hydroxyl triarylmethane), bromcresol purple (BCP; The hydroxyl triarylmethane), bromthymol blue (BTB, hydroxyl triarylmethane), blue (Phloxine Blue) (PB, the fluorone) of phloxin, thymol blue (TB; The hydroxyl triarylmethane) or m-cresol purple (MCP, hydroxyl triarylmethane).
In another embodiment, at least a reactive dye can be oxygen sensitive property reactive dye.The indicator that comprises at least a oxygen sensitive property reactive dye can be colorimetric indicator or light emitting-type indicator.
At least a oxygen sensitive property reactive dye can be; Methylenum careuleum (MB for example; Thiazine), thionine (Th; Thiazine), reddish black B (AzB, thiazine), Nile blue (NR,
Figure BDA00001769902500061
piperazine) or after reduction to any other dyestuff of oxygen sensitive.This reduction can use semiconductor light-catalyst such as titania to carry out photochemically, perhaps uses reductive agent such as ascorbic acid chemically to carry out.Reactive dye also can be that represent can be by the dyestuff of the fluorescence of oxygen quencher; As tris (bipyridine) ruthenium (Ruthenium tris bypyridyl) (Rubpp, metal complex), three (4,7-diphenyl-1; The 10-phenanthroline) perchloric acid ruthenium (II) (Rudpp; Metal complex), octaethylporphyrin ketone platinum (II) (PtOEPK, metal complex), proflavin (Pf, proflavin).
In one embodiment, this chemical indicator can comprise the reactive dye more than a type.Through such setting, this chemical indicator can detect the existence more than one type analyte, and/or can or detect the variation of particular analysis substrate concentration, for example changes the reactive dye of color down through the variable concentrations that is provided at specific analyte.
According to a further aspect in the invention; The method for preparing chemical indicator is provided; Said method comprises at least a reactive dye or China ink is dissolved at least a solvent; It is mixed with the particle inorganic matrix, thereby and evaporate at least a solvent and form and comprise at least a reactive dye that are applied and/or are immersed into wherein or the particle inorganic matrix of China ink.
Should understand that at least a solvent can dissolve at least a reactive dye or China ink usually, but can not dissolve the particle inorganic matrix of typically processing usually by insoluble material.The particle inorganic matrix typically comprises for example inorganic filler and/or inorganic pigment, and it can be white, transparent or colored.
Preferably, this method can comprise with powder type provides the particle inorganic matrix.
Typically, this method can also comprise stirring and/or sonicated.
Preferably, at least a solvent can be organic solvent, for example methyl alcohol.In this case, at least a reactive dye or China ink typically can be solvent-soluble dye.
Alternatively, at least a can the comprising at least a solvent, for example, water.In this case, at least a reactive dye or China ink typically can be water-soluble dyes.
Typically, chemical indicator can be as the present invention aforementioned aspect described in chemical indicator.
According to a further aspect in the invention; A kind of polymer composites is provided; Said polymer composites comprises at least a thermoplastic polymer and at least a chemical indicator; Said at least a chemical indicator comprises particle inorganic matrix and at least a chemical indicator, and said at least a chemical indicator is coated on the particle inorganic matrix and/or is immersed in the particle inorganic matrix.
At least a chemical indicator can comprise as about aforementioned aspect of the present invention and the described chemical indicator of relative embodiment.
Advantageously, at least a chemical indicator can have high thermal stability, and for example about at least 80 ℃, preferably at least 110 ℃.Through such setting, even for example be exposed to through after the higher temperature of extruding, being applied in calendering and/or molded processing and/or the production run, this polymer composites still can represent outstanding sensing capability.
Advantageously, chemical indicator can be dark but all be to have the storage stability that lives forever under the condition of environmental baseline aspect other, for example at least one week, preferred at least one month, more preferably at least six months, most preferably at least ten two months.
Typically, at least a chemical indicator can be dispersed at least a polymkeric substance.
Advantageously, at least a chemical indicator can be substantially uniformly dispersed at least a polymkeric substance.
Polymer composites can comprise through melt-processed, the preferred polymer composites through extruding, and can following form providing: for example film, sheet, pipe or any other suitable configuration.
Preferably, at least a thermoplastic polymer can comprise addition polymer such as polyolefin, for example tygon or polypropylene, or other thermoplasticity addition polymers, for example polystyrene or polyacrylate.
Alternatively, at least a thermoplastic polymer can comprise condensation polymer, for example polycarbonate, polyethers, polyester, polyamide or polyacetal.
In one embodiment, at least a thermoplastic polymer can be hydrophobic polymer, for example tygon.In this case, at least a chemical indicator can comprise the hydrophobic granule inorganic matrix, for example hydrophobic silica or lyophobic alumina.Through such setting, can improve at least a chemical indicator and wherein be dispersed with the compatibility between at least a hydrophobic polymer of said at least a chemical indicator.Alternatively, at least a chemical indicator can comprise untreated particle inorganic matrix, for example untreated titania.
In another embodiment, at least a thermoplastic polymer can be hydrophilic polymer, for example polyethylene oxide.In this case, at least a chemical indicator can comprise the hydrophilic granules inorganic matrix, for example hydrophilic silicon dioxide or hydrophilic aluminium oxide.Through such setting, can improve at least a chemical indicator and wherein be dispersed with the compatibility between at least a hydrophilic polymer of said at least a chemical indicator.Alternatively, at least a chemical indicator can comprise untreated particle inorganic matrix, for example untreated titania.
In one embodiment, polymer composites can comprise the chemical indicator more than a type.Through such setting, polymer composites can detect more than a kind of analyte and/or can or detect the change in concentration of specific analyte, for example changes the chemical indicator of color through the variable concentrations that is provided at specific analyte.
According to a further aspect in the invention, the method for preparing polymer composites is provided, said method comprises to be provided as about aforementioned aspect of the present invention and the described at least a chemical indicator of relative embodiment at least a thermoplastic polymer.
This method can comprise mixes at least a chemical indicator of at least a thermoplastic polymer with pulverised form (for example powder).
This method can also comprise grinds at least a thermoplastic polymer with at least a chemical indicator.
Preferably, this method can comprise at least a chemical indicator is dispersed at least a thermoplastic polymer, for example through fusion.
Typically, this method can comprise the step for preparing polymer composites, and said step comprises the for example said polymer composites of melt-processed.
Preferably, preparation process can comprise for example film, sheet, pipe or other suitable configuration are extruded or be molded as to polymer composites.
Can before preparation process, carry out for example at least a chemical indicator being dispersed in the process at least a thermoplastic polymer through fusion.
Alternatively, can in the process of preparation process, carry out at least a chemical indicator is dispersed in the step at least a thermoplastic polymer.
In one embodiment, this method can be included in before the preparation or mix the multiple polymers compound substance in the process of preparation, and every kind of polymer composites can detect the existence of one or more selected analytes.This method can comprise first polymer composites that for example comprises first chemical indicator that can detect first analyte and the second polymer composites blend that comprises second chemical indicator that can detect second analyte.
According to a further aspect in the invention, provide according to the polymer composites of aforementioned aspect of the present invention and relative embodiment and for example breathe the purposes in the medical science in packaging for foodstuff and/or medical science.
According to a further aspect in the invention, a kind of packaging for foodstuff goods are provided, said packaging for foodstuff goods comprise at least a polymer composites according to aforementioned aspect of the present invention and relative embodiment.
These packaging for foodstuff goods can be the goods of sealing, for example box, or open article, for example dish.
Alternatively, these packaging for foodstuff goods can be amorphous or deformable packing articles, for example packaging film such as plastics package or cling film.
In one embodiment, the packaging for foodstuff goods can comprise a plurality of different pieces, its each self-contained at least a polymer composites that can detect the existence of one or more selected analytes.These packaging for foodstuff goods can comprise the first of being processed by first polymer composites that comprises first chemical indicator that can detect first analyte (for example ammonia) at least, and the second portion of being processed by second polymer composites that comprises second chemical indicator that can detect second analyte (for example carbon dioxide, oxygen or other suitable analytes).
Each part that in one embodiment, can detect the existence of one or more selected analytes can be configured to like form that can display message (for example words or symbol) after change color.When first analyte (for example ammonia) release caused the change color of first chemical indicator, various piece can display message or words, for example " danger " or " dangerous ".Alternatively, when not having first analyte (for example ammonia), in various piece, can see information or words for example " safety ", and this information or words can disappear when first analyte discharges the change color cause first chemical indicator.
According to a further aspect in the invention, medical apparatus is provided, said medical apparatus comprises the polymer composites according to aforementioned aspect of the present invention and relative embodiment.
In one embodiment, can this medical science equipment be used for breathing medical science.
This device can be the form of for example managing like respiratory siphon.
Through such setting, the existence that said pipe itself can check and analysis thing (for example carbon dioxide), thus avoided independent sensor or indicator are matched to the needs of existing pipe assembly.This not only can improve the simplicity and the convenience of operation pipe assembly, but also has avoided because the leakage due to the existence of the additional components that links to each other with the person in charge and/or the risk of pollution.
In one embodiment, this medical apparatus can comprise a plurality of different pieces, its each self-contained at least a polymer composites that can detect the existence of one or more selected analytes.Medical apparatus can comprise; For example; The first of processing by first polymer composites that comprises first chemical indicator that can detect first analyte (for example carbon dioxide), and the second portion of processing by second polymer composites that comprises second chemical indicator that can detect second analyte.
Each part that in one embodiment, can detect the existence of one or more selected analytes can be configured to like form that can display message (for example words or symbol) after change color.When the release of first analyte (for example carbon dioxide) caused the change color of first chemical indicator, various piece can display message or words, for example " danger " or " dangerous ".Alternatively, when not having first analyte (for example carbon dioxide), in various piece, can see information or words for example " safety ", and this information or words can disappear when first analyte discharges the change color cause first chemical indicator.
According to a further aspect in the invention; Carbon dioxide sensor or indicator are provided; It comprises the polymer composites according to aforementioned aspect of the present invention and relative embodiment; Wherein said polymer composites comprises at least a chemical indicator, and said at least a chemical indicator comprises at least a carbon dioxide sensitivity reactive dye.
In one embodiment, at least a carbon dioxide sensitivity reactive dye can comprise m-cresol purple.
In one embodiment, polymer composites can comprise at least a thermoplastic polymer, and said at least a thermoplastic polymer can comprise polyolefin, for example tygon.
According to a further aspect in the invention; Ammonia gas sensor or indicator are provided; Said ammonia gas sensor or indicator comprise the polymer composites according to aforementioned aspect of the present invention and relative embodiment; Wherein said polymer composites comprises at least a chemical indicator, and said at least a chemical indicator comprises at least a ammonia susceptibility reactive dye.
In one embodiment, at least a ammonia susceptibility reactive dye can comprise bromophenol blue.
In one embodiment, polymer composites can comprise at least a thermoplastic polymer, and said at least a thermoplastic polymer can comprise polyolefin, for example tygon.
According to a further aspect in the invention; Oxygen sensor or indicator are provided; Said oxygen sensor or indicator comprise the polymer composites according to aforementioned aspect of the present invention and relative embodiment; Wherein said polymer composites comprises at least a chemical indicator, and said at least a chemical indicator comprises at least a oxygen sensitive property reactive dye.
In one embodiment, at least a oxygen sensitive property reactive dye can comprise colorimetric type dye such as methylenum careuleum.
In another embodiment, at least a oxygen sensitive property reactive dye can comprise light emitting-type dyestuff such as Rudpp.
In one embodiment, polymer composites can comprise at least a thermoplastic polymer, and said at least a thermoplastic polymer can comprise polyolefin, for example tygon.
The accompanying drawing summary
To only provide embodiment of the present invention through the mode of instance and according to accompanying drawing now, accompanying drawing is:
Fig. 1 form, this form have shown the CO that in the chemical indicator of preparation first embodiment according to an aspect of the present invention, uses 2The type of susceptibility reactive dye;
Fig. 2 form, this form have shown the type of the ammonia susceptibility reactive dye that in the chemical indicator of preparation second embodiment according to an aspect of the present invention, use;
Fig. 3 form, this form have shown the type of the oxygen sensitive property reactive dye that in the chemical indicator of preparation the 3rd embodiment according to an aspect of the present invention, use;
Fig. 4 photo, this photo have shown when being exposed to CO 2The time, the use MCP of first embodiment according to an aspect of the present invention is as the CO of reactive dye 2The change color of sensitive indicator;
Fig. 5 photo, this photo has showed the CO of Fig. 4 2The change color of sensitive indicator, and show (a) untreated silica, (b) be exposed to the silica pigment of carbon dioxide MCP modification before, and (c) be exposed to the silica pigment of carbon dioxide MCP modification afterwards;
Fig. 6 photo, this photo has showed the CO of Fig. 4 2The change color of sensitive indicator; And show that (a) is exposed to the silica pigment of carbon dioxide MCP modification before; (b) be exposed to the silica pigment of the MCP modification in the process of carbon dioxide, and (c) be exposed to the silica pigment of the MCP modification after the carbon dioxide;
When Fig. 7 photo, this photo had shown the carbon dioxide in being exposed to people's breathing, the use thymolphthalein of first embodiment according to an aspect of the present invention was as the CO of reactive dye 2The change color of sensitive indicator;
When Fig. 8 photo, this photo had shown the carbon dioxide in being exposed to people's breathing, the use o-cresolphthalein of first embodiment according to an aspect of the present invention was as the CO of reactive dye 2The change color of sensitive indicator;
Fig. 9 photo; This photo has showed the change color of the ammonia sensitive indicator of second embodiment according to an aspect of the present invention; And shown (a) untreated silica; (b) be exposed to the silica pigment of the BPB modification before the ammonia, and (c) be exposed to the silica pigment of the BPB modification after the ammonia;
Figure 10 photo; This photo has showed the change color of the ammonia sensitive indicator of Fig. 9; And shown that (a) is exposed to the silica pigment of the BPB modification before the ammonia, and (b), (c) with (d) in the silica pigment to the BPB modification after the exposure of ammonia of increase;
Figure 11 photo, this photo have shown that the use MB of the 3rd embodiment according to an aspect of the present invention is as solvent-borne type TiO when activating with the UV lamp and being exposed to oxygen afterwards 2The change color of the oxygen sensitive property indicator of the reactive dye in the pigment;
Figure 12 photo, this photo have shown that the use MB of the 3rd embodiment according to an aspect of the present invention is as water base TiO when activating with the UV lamp and being exposed to oxygen afterwards 2The change color of the oxygen sensitive property indicator of the reactive dye in the pigment;
Figure 13 photo, this photo have shown when being exposed to carbon dioxide, the CO of the indicator of use Fig. 4 of first embodiment according to an aspect of the present invention 2The change color of sensitive polymer composite material film;
Figure 14 is as the CO of Figure 13 of the function record of gas concentration lwevel 2The UV visible spectrum of sensitive polymer composite material film;
The CO of Figure 15 Figure 13 2The absorbance response at the 592nm place of sensitive polymer composite material film has shown three response cycle to 100% carbon dioxide and the recovery of air purge subsequently;
When Figure 16 photo, this photo have shown the 1000ppm ammonia in being exposed to nitrogen, the change color of the ammonia sensitive polymer composite material film of the indicator of use Fig. 9 of second embodiment according to an aspect of the present invention;
Under the 1000ppm ammonia of Figure 17 in nitrogen, the 600nm place of the ammonia sensitive polymer composite material film of Figure 16 be the absorbance response of function with time;
Figure 18 conduct is to the UV visible spectrum of the ammonia sensitive polymer composite material film of Figure 16 of the function record of the exposure duration of the 1000ppm ammonia in the nitrogen;
The ammonia sensitive polymer composite material film of Figure 19 Figure 16 has shown 1000ppm ammonia (lasting 1 hour) and heat has subsequently been recovered five response cycle of (lasting 2 hours at 70 ℃) in the absorbance response at 600nm place;
Figure 20 form, this form have shown the response of the ammonia sensitive polymer composite material film of the reactive dye of use Fig. 2 of according to an aspect of the present invention second embodiment and the comparison of recovery;
Figure 21 photo, this photo have shown when being exposed to oxygen, the change color of the oxygen sensitive property polymer composites film of the indicator of use Figure 11 of the 3rd embodiment according to an aspect of the present invention; And
Figure 22 photo, this photo have shown when being exposed to oxygen, the change color of the oxygen sensitive property polymer composites film of the indicator of use Figure 12 of the 3rd embodiment according to an aspect of the present invention.
Embodiment
Preparation
Select silicon dioxide (silicon dioxide) and aluminium oxide (aluminium oxide) as the inorganic matrix that is used to prepare indicator.Find that silica pigment is especially suitable inorganic matrix, reason is its widespread use as polymer filler, low cost, is easy to get, is prone to processing, security and lacks color (white).Both prepare indicator to use hydrophobic pigment (silicon dioxide or aluminium oxide) and hydrophilic pigment (silicon dioxide or aluminium oxide).
Also titania is used in combination in the preparation of oxygen sensitive property indicator.Selecting titania is because it is a semiconductor material, thereby it can serve as photocatalyst and the specific oxygen sensitive property dyestuff of activation in the reduction.
The various active dyestuff is used to prepare indicator.In various situation, based on the material that will detect select dyestuff.The form that provides among Fig. 1,2 and 3 has shown the dyestuff that is used to prepare carbon dioxide sensitivity indicator, ammonia sensitive indicator and oxygen sensitive property indicator respectively.
Be used for CO 2The hydrophobic silica of indicator or aluminium oxide
About 0.04g reactive dye are added to contain 2.0g hydrophobic silica (Degussa/Evonik Aerosil R812; S.S.A.=260+/-30m 2/ g; In the beaker of particle mean size=7nm) and about 100mL methyl alcohol.1M TBAH in the methyl alcohol of adding 1mL.Potpourri is fully stirred/sonicated, resulting solution is transferred to round-bottomed flask and under vacuum, removes methyl alcohol at 30 ℃ by rotary evaporator.Shift out and use pestle and mortar that its grinding is fine powder in the powder of gained.
Equally, as above prepare pigment, and prove that it is effective equally based on lyophobic alumina (Degussa/Evonik Aeroxide Alu C805) rather than silicon dioxide.
Except that TBAH, also alternative alkali be can use, NaOH and soda mint comprised.
Except that methyl alcohol, also alternative solvent be can use, ethanol and ethyl acetate comprised.
Be used for CO 2The hydrophilic silicon dioxide of indicator or aluminium oxide
Typically, use lower dyestuff and inorganic pigment ratio with hydrophilic silicon dioxide (Degussa/Evonik Aerosil 300) and hydrophilic aluminium oxide (Degussa/EvonikAeroxide Alu C).
The reactive dye that add 0.12g to 15.0g hydrophilic silicon dioxide (Degussa/Evonik Aerosil 300).Add the 1.5M TBAH in the water of about 100mL water and 12mL.After stirring, with solvent (water) vapourisation under reduced pressure with the preparation fine powder.
Equally, as above prepare pigment, and prove that it is effective equally based on hydrophilic aluminium oxide (Degussa/Evonik Aeroxide Alu C) rather than silicon dioxide.
Be used for NH 3The hydrophobic silica of indicator or aluminium oxide
About 1g reactive dye are added to hydrophobic silica (the Degussa/Evonik Aerosil R812 that contains 4.0g; S.S.A.=260+/-30m 2/ g; In the beaker of particle mean size=7nm) and the about methyl alcohol of 80mL.Potpourri is fully stirred/sonicated, resulting solution is transferred to round-bottomed flask, and under vacuum, remove methyl alcohol by rotary evaporator at 30 ℃.Take out and use pestle and mortar that its grinding is fine powder in the powder of gained.
Equally, as above prepare pigment, prove that it is effective equally based on lyophobic alumina (Degussa/Evonik Aeroxide Alu C805) rather than silicon dioxide.
Be used for NH 3The hydrophilic silicon dioxide of indicator or aluminium oxide
Typically, use lower dyestuff and inorganic pigment ratio with hydrophilic silicon dioxide (Degussa/Evonik Aerosil 300) and hydrophilic aluminium oxide (Degussa/EvonikAeroxide Alu C).
About 0.5g reactive dye are added in the beaker that comprises 4.0g hydrophilic silicon dioxide (Degussa/Evonik Aerosil 300) and about 80mL water.Potpourri is fully stirred/sonicated, resulting solution is transferred to round-bottomed flask and it removes desolvate (water) by rotary evaporation at 30 ℃ under vacuum.The powder of gained is taken out and uses pestle and mortar to be ground into fine powder.
Equally, as above prepare pigment, and prove that it is effective equally based on hydrophilic aluminium oxide (Degussa/Evonik Aeroxide Alu C) rather than silicon dioxide.
Be used for light emitting-type O 2The hydrophobic silica of indicator or aluminium oxide
With the 2.0g hydrophobic silica (Degussa/Evonik Aerosil R812, S.S.A.=260+/-30m 2/ g, particle mean size=7nm), 2mg oxygen sensitive property luminescent dye such as PtOEPK or Rudpp (tetraphenyl borate salts) join the suitable solvent (be used for the THF of PtOEPK or be used for the acetone of Rudpp) of 100mL.Potpourri is fully mixed and under reduced pressure uses rotary evaporator to remove and desolvate.Shift out and use pestle and mortar to be ground into fine powder in resulting powder.
Equally, as above prepare pigment, and prove that it is effective equally based on lyophobic alumina (Degussa/Evonik Aeroxide Alu C805) rather than silicon dioxide.
Be used for light emitting-type O 2The hydrophilic silicon dioxide of indicator or aluminium oxide
2.0g hydrophilic silicon dioxide (Degussa/Evonik Aerosil 300), 2mg oxygen sensitive property luminescent dye such as Rudpp (chloride salt) are added in the polar solvent such as ethanol or water of 100mL.Potpourri is fully mixed and under the pressure that reduces, uses Rotary Evaporators to remove and desolvate.The powder of gained is taken out and uses pestle and mortar to be ground into fine powder.
Equally, as above prepare pigment, and prove that it is effective equally based on hydrophilic aluminium oxide (Degussa/Evonik Aeroxide Alu C) rather than silicon dioxide.
Titania
In the preparation of oxygen sensitive property indicator, be used in combination titania.Select titania to be because it is the photocatalyst and the therefore semiconductor material of the specific oxygen sensitive property dyestuff of activation that can serve as in the reduction under specific grade.Also want to order about the photo-reduction of dyestuff to oxygen sensitive form because titania must not only can serve as carrier, the titanium oxide inorganic matrix of selecting the form that is untreated is so that keep its photocatalysis property.
Be used for O 2The solvent-borne type pigment of indicator
Add 10mg reactive dye, 1.0gDL-Threitol and about 100mL ethanol to 2.0g titania (Degussa/Evonik P25).Potpourri is fully mixed and under the pressure that reduces, uses Rotary Evaporators to remove desolvate (ethanol) afterwards.The powder of gained is taken out and uses pestle and mortar to be ground into fine powder.
Be used for O 2The water-base pigment of indicator
Add 10mg reactive dye, 1.0gDL-Threitol and about 100mL water to 2.0g titania (Degussa/Evonik P25).Potpourri is fully mixed and under the pressure that reduces, uses Rotary Evaporators to remove desolvate (water) afterwards.The powder of gained is taken out and uses mortar and pestle to be ground into fine powder.
Be combined in the polymkeric substance
A) hydrophobic polymer
Select tygon as especially suitable hydrophobic polymer, owing to its low cost, easy preparation and processing and wide range of application, said range of application comprises packaging for foodstuff and medical application.
For compatible with tygon, the indicator that is used for being bonded to this polymer film is based on the indicator of hydrophobic silica, lyophobic alumina or untreated titania.
Typically, the hydrophobic indicator of 0.4g is added to the powdery polyethylene of 2.0-4.0g.Two kinds of powder further are ground to color even.Use Specac Atlas TMThe series hot plate under 5 tons pressure with the sample of gained powder 115 ℃ of hot pressing 5 minutes, make its cooling afterwards.Obtain the thick plastic foil of 0.1mm.
This program is similar in preparation and wherein is dispersed with the program of using in the polymer film of extruding of pigment, therefore produces extremely thin polymer film.
B) hydrophilic polymer
Select polyethylene oxide as suitable hydrophilic polymer.
For compatible, be used for being bonded to the indicator that indicator that this polymer film uses is based on hydrophilic silicon dioxide, hydrophilic aluminium oxide or untreated titania with polyethylene oxide.
Typically, the hydrophilic indicator of 0.4g is added to the Powdered polyethylene oxide of 2.0-4.0g.Two kinds of powder further are ground to color even.Use Specac Atlas TMThe series hot plate under 5 tons of pressure with the sample of gained powder 65 ℃ of hot pressing 5 minutes, make its cooling afterwards.Obtain the thick plastic foil of 0.1mm.
The result
The character of indicator
A) carbon dioxide indicator
Use the dyestuff of listing among Fig. 1 as being used to prepare CO 2The CO of indicator 2The susceptibility reactive dye.Employed main dyestuff is m-cresol purple (MCP).Hydrophobic and hydrophilic silicon dioxide pigment through method for preparing MCP modification also obtains blue fine powder.
Like Fig. 4, shown in 5 and 6, in case be exposed to carbon dioxide, sapphirine 1 pigment becomes glassy yellow 2 immediately.Change color is a completely reversibility.Along with concentration of carbon dioxide reduces, pigment becomes its blueness 1 color originally gradually again.
To based on hydrophobic and indicator hydrophilic silicon dioxide pigment, use the Olympus SZ11 microscope that is equipped with the DP12 digital camera on particle scale, to examine under a microscope the change color of the silica pigment of MCP modification.Under the situation of using hydrophilic silicon dioxide crystal (the about 100 μ m of average crystalline size), the magnification of x220 most clearly shows the change color of monocrystalline.The crystal of hydrophobic silica pigment is littler significantly, so the change color of single crystal is sightless under this magnification.Yet, observe clearly change color of whole crystalline matrix.
Find that this indicator is highly stable, even also not loss of performance after being to store 8 months in the glass jar.This is unexpected, because can't foresee reactive dye such as MCP is coated with or is immersed into the stability that will improve this dyestuff on the silica pigment significantly.
Fig. 7 and 8 has described CO 2The alternative embodiment of susceptibility pigment, and show the effect of breathing activation to this indicator.
Indicator shown in Fig. 7 is based on the hydrophobic silica pigment with the thymolphthalein modification.In case be exposed to the carbon dioxide (being generally 5%) that contains in the human breathing, sapphirine 3 pigment become colorless 4 immediately.Change color is a completely reversibility.After under nitrogen, purging, pigment becomes its blueness 3 colors originally gradually again.
Indicator shown in Fig. 8 is based on the hydrophobic silica pigment with the o-cresolphthalein modification.In case be exposed to carbon dioxide contained in the human breathing, purple 5 pigment become colorless 4 immediately.Change color is a completely reversibility.Under normal atmosphere, pigment becomes its purple 5 colors originally gradually again.
B) ammonia indicator
Use the dyestuff of listing among Fig. 2 as the NH that is used to prepare the ammonia indicator 3The susceptibility reactive dye.All these dyestuffs (except that phloxin B (PB)) all are the hydroxyl triarylmethane dyes, and more specifically, sulfonephthalein.These are typical pH indicator dyes of time experience deprotonation in being placed on sufficient alkaline environment.This deprotonation causes maximum wavelength (λ on the absorption spectrum Maximum) move.
Employed main dyestuff is bromophenol blue (BPB), and its structure is as follows:
Figure BDA00001769902500181
BPB has 4.10 pK aAnd experience λ Max600nm from the 430nm of its yellow acid form to its blue alkaline form moves.
Hydrophobic and hydrophilic silicon dioxide pigment through method for preparing BPB modification also obtains orange fine powder.
Thereby the ammonia indicator of preparation is exposed to the top of 25% ammonia solution.
Shown in Fig. 9 and 10, in case increase the exposure to ammonia, bright orange 6 pigment become reddish brown 7, green 8 and final blueness 9.
To based on hydrophobic and indicator hydrophilic silicon dioxide pigment, use the Olympus SZ11 microscope that is equipped with the DP12 digital camera on particle scale, to examine under a microscope the change color of the silica pigment of BPB modification.Under the situation of using hydrophilic silicon dioxide crystal (the about 100 μ m of average crystalline size), the magnification of x220 most clearly shows the change color of monocrystalline.The crystal of hydrophobic silica pigment is littler significantly, so the change color of single crystal is sightless under this magnification.Yet, observe clearly change color of whole crystalline matrix.
Find that this indicator is highly stable, even also not loss of performance after being to store 6 months in the glass jar.This is unexpected, because can't foresee reactive dye such as BPB is coated with or is immersed into the stability that will improve this dyestuff on the silica pigment significantly.
C) oxygen indicator
Use the dyestuff of listing among Fig. 3 as the O that is used to prepare oxygen indicator 2The susceptibility reactive dye.Oxygen indicator be light emitting-type or than colour pattern.
Employed main colorimetric oxygen sensitive property dyestuff is MB.TiO 2 pigment through method for preparing MB modification and obtain blue fine powder.
Use is equipped with the Olympus SZ11 microscope of DP12 digital camera on particle scale, to examine under a microscope the change color of the silica pigment of MB modification.Figure 11 relates to solvent-borne type MB/TiO 2/ DL-threitol pigment, and Figure 12 relates to water base MB/TiO 2/ DL-threitol pigment.
Shown in Figure 11 and 12, after being exposed to about 1 minute of UVA radiation, light blue 14 pigment become colorless 15.After being exposed to airborne oxygen, change color is a completely reversibility.Along with dyestuff by gox oxidation again, pigment becomes its original blueness 14 colors gradually again.
Used main light emitting-type oxygen sensitive property dyestuff is Rudpp, through making the Rudpp solvent that becomes solvable with the pairing of lipophilicity counter ion counterionsl gegenions such as tetraphenyl borate ion.
Find that this indicator is highly stable, even also not loss of performance after in glass jar, storing 12 months.This is unexpected, because can't foresee reactive dye such as Rudpp or MB coating or be immersed into the stability that will improve this dyestuff on the silica pigment significantly.
The character of polymer film
With indicator be bonded to mean in polymer film such as the polyethylene film make the polymer film of extruding have the induction character ability.Yet, unclear be indicator based on very unsettled reactive dye whether can stand to be incorporated in in the polymkeric substance and subsequently processing to polymer composites via known method.
A) carbon dioxide indicator
Be bonded in the tygon through the hydrophobic silica pigment of said method the MCP modification.Obtain the thick blue plastic foil of about 0.1mm.This film is exposed to carbon dioxide, and observes resulting change color.
As shown in Figure 13, in case be exposed to carbon dioxide, that blue 1 ' film becomes is yellow 2 '.Change color is a completely reversibility.Along with concentration of carbon dioxide reduces, film becomes its blueness 1 color originally gradually again.
As shown in Figure 14, the maximum absorption wavelength of plastic foil is %CO in the ambient atmosphere 2Function.Can find out that maximum absorption wavelength moves to 424nm from 592nm along with dyestuff becomes its protonated form from its deprotonation form.Important ground, the sensitivity of finding this plastic foil is outstanding.As shown in Figure 14, be low to moderate 2%CO containing 2Environment in, maximum absorption wavelength moves to 424nm by 592.
Through film is exposed to 100%CO 2, afterwards with air purge to study repeatability.Select 100%CO 2To be used for this group experiment, reason is that the response ratio of plastic foil indicator is at the CO that uses low concentration 2The time fast.As shown in Figure 15, find CO 2The performance of susceptibility plastic foil indicator is not impaired after 3 circulations that are exposed to carbon dioxide and air purge, and sensitivity and restorative both are uninfluenced.
B) ammonia indicator
Be bonded in the tygon through the hydrophobic silica pigment of said method the BPB modification.Obtain the thick orange-yellow plastic foil of about 0.1mm.This film is exposed to the 1000ppm ammonia in the nitrogen, and observes resulting change color.
As shown in Figure 16, in case be exposed to ammonia, that orange-yellow 10 ' film becomes is blue 9 '.This change color is a completely reversibility.
As shown in Figure 17, observed change color is progressive under this condition.This film gradually by orange-yellow 10 ' become bright green 11 ', blue-green 12 ', dark blue-green 13 ' and final blueness 9 '.
As shown in Figure 18, the maximum absorption wavelength of plastic foil is the function that is exposed to the time of the ammonia in the ambient atmosphere.Can find out that maximum absorption wavelength moves to about 600nm from about 420 along with dyestuff becomes its second chemical species from its first chemical species.
Even find to carry out extra nitrogen purging, BPB type ammonia susceptibility plastic foil indicator also recovers slowly under environmental baseline.Yet, to find to pass through at about 70 ℃ of heating films, the restore cycle shortens greatly.As shown in Figure 19, find that the performance of BPB type ammonia susceptibility plastic foil indicator is not impaired after 5 circulations that are exposed to ammonia and heat recovery, sensitivity and restorative both are uninfluenced.
All seven kinds of ammonia susceptibility reactive dye for listing among Fig. 2 are further studied.1000ppm ammonia with in the nitrogen is tested film, and exposure duration is 1 hour.Provide in the table of comparison in Figure 20 to response and recovery characteristics.Can observe, it is different to the response that is exposed to ammonia with under environmental baseline, recover to use the different activities dyestuff to produce in the indicator pigment in being provided at corresponding ammonia induction plastic foil.Therefore, can be adapted to use the dyestuff of particular type for the desired application of corresponding indicator.For example, in packaging for foodstuff, the food releases volatile amine that rots is slow and progressive process, and therefore fast the but clearly visible response expection of appropriateness is gratifying.Yet, use as monitor in the chemical environment at other, for example in the laboratory, response possibly be a key parameter fast.
C) oxygen indicator
Be bonded in the tygon through the TiO 2 pigment of said method the MB modification.Obtain the thick blue plastic foil of about 0.1mm.Under nitrogen through this film being bleached about 1 minute with the UV rayed.Afterwards it is exposed to oxygen, and observes resulting color restoration.
Figure 21 relates to the solvent-borne type MB/TiO in the tygon 2/ DL-threitol pigment, and Figure 22 relates to the water base MB/TiO in the polyethylene oxide 2/ DL-threitol pigment.
Shown in Figure 21 and 22, under nitrogen, be exposed to after wide about 4 to 5 minutes of the UVA, blue 14 ' film becomes colorless 15 '.After being exposed to airborne oxygen, the change color completely reversibility changes.After dyestuff was reoxidized by gox, this film became its indigo plant 14 ' color originally gradually again.
Also tested the typical light emitting-type indicator plastic foil (not providing) that uses the TiO 2 pigment of Rudpp modification.Along with oxygen level raises, this film represents the luminous of minimizing.

Claims (39)

1. polymer composites; Said polymer composites comprises at least a thermoplastic polymer and at least a chemical indicator; Said at least a chemical indicator comprises particle inorganic matrix and at least a reactive dye or China ink, and said at least a reactive dye or China ink are coated on the said particle inorganic matrix and/or are immersed in the said particle inorganic matrix.
2. polymer composites according to claim 1, wherein said at least a chemical indicator is evenly dispersed in the said at least a thermoplastic polymer basically.
3. according to claim 1 or the described polymer composites of claim 2, wherein said polymer composites is melted the following form that is processed into: film, sheet, pipe or any other suitable configuration.
4. according to each the described polymer composites in the aforementioned claim, wherein said chemical indicator has about at least 80 ℃, preferred at least 110 ℃ thermal stability.
5. according to each the described polymer composites in the claim 1 to 4, wherein said at least a thermoplastic polymer comprises and is selected from polyolefin such as poly addition polymer, or the thermoplasticity addition polymer such as the polystyrene of other types.
6. according to each the described polymer composites in the claim 1 to 4, wherein said at least a thermoplastic polymer comprises condensation polymer such as polycarbonate, polyethers, polyester, polyamide and/or polyacetal.
7. according to each the described polymer composites in the claim 1 to 6; Wherein said at least a thermoplastic polymer comprises hydrophobic polymer, and said at least a chemical indicator comprises hydrophobic granule inorganic matrix or untreated particle inorganic matrix.
8. according to each the described polymer composites in the claim 1 to 6; Wherein said at least a thermoplastic polymer comprises hydrophilic polymer, and said at least a chemical indicator comprises hydrophilic granules inorganic matrix or untreated particle inorganic matrix.
9. according to each the described polymer composites in the aforementioned claim, wherein said polymer composites comprises the chemical indicator more than a type.
10. method for preparing according to each the described polymer composites in the claim 1 to 9; Said method comprises provides at least a chemical indicator at least a polymkeric substance; Said at least a chemical indicator comprises particle inorganic matrix and at least a reactive dye or China ink, and said at least a reactive dye or China ink are coated on the said particle inorganic matrix and/or are immersed in the said particle inorganic matrix.
11. method according to claim 10, said method comprise said at least a polymkeric substance is ground with said at least a chemical indicator, and/or said at least a chemical indicator is dispersed in the said at least a polymkeric substance.
12. according to claim 10 or the described method of claim 11, said method comprises through melt-processed, extrudes and/or the said polymer composites of molded preparation.
13. method according to claim 12; Said method is included in before the preparation or in the process of preparation, mixes multiplely according to each polymer composites in the claim 1 to 9, and every kind of polymer composites can detect the existence of one or more selected analytes.
14. for example breathe the purposes in the medical science in packaging for foodstuff and/or medical science according to each polymer composites in the claim 1 to 9.
15. packaging for foodstuff goods, said packaging for foodstuff goods comprise at least a according to each the described polymer composites in the claim 1 to 9.
16. packaging for foodstuff goods according to claim 15; Said packaging for foodstuff goods comprise the part that at least one is processed by first polymer composites; Said first polymer composites comprises at least a chemical indicator, and said at least a chemical indicator comprises at least a carbon dioxide sensitivity reactive dye; At least one is by the part that second polymer composites is processed, and said second polymer composites comprises at least a chemical indicator, and said at least a chemical indicator comprises at least a ammonia susceptibility reactive dye; And/or at least one part of processing by the polymer compound substance, said polymer compound substance comprises at least a chemical indicator, and said at least a chemical indicator comprises at least a oxygen sensitive property reactive dye.
17. a medical treatment device, said medical treatment device comprise at least a according to each the described polymer composites in the claim 1 to 9.
18. comprising, the described medical treatment device of claim 17, said medical treatment device breathe medical device such as respiratory siphon.
19. according to each the described medical treatment device in the claim 17 to 18; Said medical treatment device comprises the part that at least one is processed by polymer composites; Said polymer composites comprises at least a chemical indicator, and said at least a chemical indicator comprises at least a carbon dioxide sensitivity reactive dye.
20. according to each the described packaging for foodstuff goods in the claim 15 to 16; Or according to each the described medical treatment device in the claim 17 to 19; Said packaging for foodstuff goods or said medical treatment device comprise a plurality of different pieces, each self-contained at least a polymer composites that can detect the existence of one or more selected analytes of said a plurality of different pieces.
21. carbon dioxide sensor or indicator; Said carbon dioxide sensor or indicator comprise according to each the described polymer composites in the claim 1 to 9; Wherein said polymer composites comprises at least a chemical indicator, and said at least a chemical indicator comprises at least a carbon dioxide sensitivity reactive dye.
22. described carbon dioxide sensor of claim 21 or indicator, wherein said at least a carbon dioxide sensitivity reactive dye comprise m-cresol purple.
23. ammonia gas sensor or indicator; Said ammonia gas sensor or indicator comprise according to each the described polymer composites in the claim 1 to 9; Wherein said polymer composites comprises at least a chemical indicator, and said at least a chemical indicator comprises at least a ammonia susceptibility reactive dye.
24. described ammonia gas sensor of claim 23 or indicator, wherein said at least a ammonia susceptibility reactive dye comprise bromophenol blue.
25. oxygen sensor or indicator; Said oxygen sensor or indicator comprise according to each the described polymer composites in the claim 1 to 9; Wherein said polymer composites comprises at least a chemical indicator, and said at least a chemical indicator comprises at least a oxygen sensitive property reactive dye.
26. described oxygen sensor of claim 25 or indicator, wherein said at least a oxygen sensitive property reactive dye comprise methylenum careuleum or Rudpp.
27. chemical indicator; Said chemical indicator comprises hydrophobic granule inorganic matrix and at least a reactive dye or China ink, and said at least a reactive dye or China ink are coated on the said hydrophobic granule inorganic matrix and/or are immersed in the said hydrophobic granule inorganic matrix.
28. the described chemical indicator of claim 27, wherein said chemical indicator have about at least 80 ℃, preferred at least 110 ℃ thermal stability.
29. the described chemical indicator of claim 27 or claim 28, wherein said chemical indicator have at least one week, preferably at least one month, more preferably at least six months, at least ten two months storage stability most preferably under dark, environmental baseline.
30. according to each the described chemical indicator in the claim 27 to 29, wherein said indicator comprises than colour pattern indicator or light emitting-type indicator.
31. according to each the described chemical indicator in the claim 27 to 30, wherein said hydrophobic granule inorganic matrix is a powder type.
32. according to each the described chemical indicator in the claim 27 to 31, wherein said hydrophobic granule inorganic matrix comprises the inorganic pigment that is selected from the following: silicon dioxide, titania, aluminium oxide, magnesium oxide, calcium oxide or zeolite.
33. according to each the described chemical indicator in the claim 27 to 32; Wherein said at least a reactive dye comprise: carbon dioxide sensitivity reactive dye such as m-cresol purple (MCP; The hydroxyl triarylmethane), thymolphthalein (3; Two (4-hydroxy-2-methyl-5-third-2-base phenyl)-2-coumarone-1-ketone of 3-), o-cresolphthalein, acryloyl group fluorescein (AcFl), β-Jia Jisanxingtong (BMUB), bromthymol blue (BTB; The hydroxyl triarylmethane), 5 ' and 6 '-carboxyl half naphthols fluorescein (c-SNAFL), 5 ' and 6 '-carboxyl half naphthols rhodamine (c-SNARF), cresol red (CR, o-cresolsulfon-phthalein), cetyltrimethyl ammonium kation (CTA +), cetyltrimethylammonium hydroxide (CTAH), two lumophore benchmark (DLR), 2-(2,4-dinitrophenyl azo)-1-naphthols-3,6 disulfonic acid (DNPA), three (TTA) europium (III) ([Eu (tta) 3]), fluorescein (Fl, resorcinol phthalein), umbelliferone-4-acetate (HCA), 1, hydroxyl pyrene-3; 6; 8-trisulfonic acid (HPTS), dimethyl diaminophenazine chloride (NR, stilbene is red), phenol red (PR, phenolsulfonphthalein), rhodamine 6G (R6G), sulfo group rhodamine 101 (SRh), thymol blue (TB; Thymolsulfonphthalein), Texas Red hydrazine (THR), and/or any other pH susceptibility dyestuff or China ink.
34. according to each the described chemical indicator in the claim 27 to 32; Wherein said at least a reactive dye comprise ammonia susceptibility reactive dye such as bromophenol blue (BPB; The hydroxyl triarylmethane), bromcresol green (BCG, hydroxyl triarylmethane), bromcresol purple (BCP, hydroxyl triarylmethane), bromthymol blue (BTB; The hydroxyl triarylmethane), the blue (PB of phloxin; Fluorone), thymol blue (TB, hydroxyl triarylmethane) and/or m-cresol purple (MCP, hydroxyl triarylmethane).
35. according to each the described chemical indicator in the claim 27 to 32, wherein said at least a reactive dye comprise oxygen sensitive property reactive dye such as methylenum careuleum (MB, thiazine), thionine (Th; Thiazine), reddish black B (AzB; Thiazine), Nile blue (NR,
Figure FDA00001769902400041
piperazine), tris (bipyridine) ruthenium (Rubpp, metal complex), three (4; 7-diphenyl-1; The 10-phenanthroline) perchloric acid ruthenium (II) (Rudpp, metal complex), octaethylporphyrin ketone platinum (II) (PtOEPK, metal complex), proflavin (Pf; Proflavin); Or any other dyestuff that after reduction, has oxygen sensitive property, and/or represent by the dyestuff of the fluorescence of oxygen quencher, close ruthenium (II) or four octyl group pyridine radicals porphyrin platinum like the dichloro terpyridyl.
36. according to each the described chemical indicator in the claim 27 to 35, wherein said chemical indicator comprises the reactive dye more than a type.
37. method for preparing according to each described chemical indicator in the claim 27 to 36; Said method comprises at least a reactive dye or China ink is dissolved at least a solvent; It is mixed with the hydrophobic granule inorganic matrix, and evaporate said at least a solvent comprises at least a reactive dye that are applied and/or are immersed into wherein or China ink with formation hydrophobic granule inorganic matrix.
38. according to the described method of claim 37, wherein said at least a solvent comprises that organic solvent and said at least a reactive dye or China ink comprise solvent-soluble dye.
39. according to the described method of claim 37, at least a water that comprises in the wherein said at least a solvent, and said at least a reactive dye or China ink comprise water-soluble dye.
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